Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst

A technology of alkyl aluminum chloride and combined catalyst is applied in the field of olefin catalytic polymerization to achieve the effects of cost reduction, good stability and high activity

Inactive Publication Date: 2015-09-23
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the catalyst is activated by methylalumoxane (MAO) or modified methylalumoxane (MMAO) to catalyze ethylene polymerization, and the polymerization activity is 1.08 to 5.55×10 5 g[mol(Ni)h] -1 , the activity is low, and the polymerization activity needs to be further improved in order to be better used in industrial production

Method used

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  • Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst
  • Ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Polymerization of ethylene under normal pressure is carried out under anhydrous and oxygen-free conditions. At 60° C. and an ethylene pressure of 0.1 MPa, 40 mL of n-heptane (for polymerization) was injected into a 100 mL Schlenk bottle, and then 2.0 mmol of diethylaluminum monochloride was injected thereinto. Dissolve 10 μmol of procatalyst 4b (that is, R in the molecular formula is isopropyl) with 10 mL of toluene, and pour it into a Schlenk bottle (control the Al / Ni ratio to 200). After half an hour of polymerization, quickly drop the polymer solution into acidified methanol or acetone solution with a rubber dropper for precipitation, filter the polymer, then wash with methanol or acetone several times, and vacuum dry at 50°C to constant weight Weighed 6.7 grams of polymer. The catalyst activity is 1.34×10 6 g[mol(Ni)h]-1, the weight average molecular weight of the polymerization product is 149kg / mol, and the polydispersity coefficient is 1.9. 1 The degree of bran...

Embodiment 2

[0026] The cocatalyst monochlorodiethylaluminum was replaced by sesquiethylaluminum chloride, and other conditions and the polymer treatment method were the same as in Example 1 to obtain 6.6 grams of polymer. The catalyst activity is 1.32×10 6 g[mol(Ni)h] -1 , the weight average molecular weight of the polymerization product is 125kg / mol, and the polydispersity coefficient is 1.9. 1 The degree of branching of the polymer as determined by H-NMR was 125 / 1000 carbon atoms.

Embodiment 3

[0028] The cocatalyst monochlorodiethylaluminum was replaced by dichloroethylaluminum, and other conditions and polymer treatment methods were the same as in Example 1 to obtain 7.4 grams of polymer. The catalyst activity is 1.48×10 6 g[mol(Ni)h] -1 , the weight average molecular weight of the polymerization product is 64kg / mol, and the polydispersity coefficient is 1.7. 1 The degree of branching of the polymer as determined by H-NMR was 124 / 1000 carbon atoms.

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Abstract

The invention relates to the field of catalytic polymerization of olefins, aiming at providing an ethylene acenaphthylene (alpha-diimine) nickel complex/alkyl aluminum chloride combined catalyst. The combined catalyst consists of an ethylene acenaphthylene (alpha-diimine) nickel complex and alkyl aluminum chloride, wherein the molar ratio of aluminum in alkyl aluminum chloride to nickel in the ethylene acenaphthylene (alpha-diimine) nickel complex is 20-800:1. Compared with the prior art, the combined catalyst provided by the invention has higher activity and better stability in catalyzing polymerization of ethylene and propene. According to the invention, alkyl aluminum chloride is used as a cocatalyst. Compared with that of using methylaluminoxane or modified methyl aluminoxane, cost is significantly reduced, and in addition, localization of alkyl aluminum chloride is realized, saving the need of importing.

Description

technical field [0001] The invention relates to the field of catalytic polymerization of olefins, in particular to an ethylene acenaphthene (α-diimine) nickel complex / alkylaluminum chloride composition and application thereof. Background technique [0002] Polyolefin is a basic material related to the national economy and people's livelihood, and because of its excellent performance, variety of varieties, easy availability of raw materials and low price, it is widely used in various fields such as industry, agriculture and national defense. The development and application of new catalyst systems is one of the core driving forces to promote the progress and development of the polyolefin industry, and is the key to controlling the structure and performance of polyolefin materials. [0003] In recent decades, the study of functionalized and differentiated polyolefin materials obtained by coordination polymerization has received extensive attention. In 1995, the Brookhart resea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F110/02C08F110/06C08F4/70
Inventor 傅智盛范志强臧丹丹
Owner ZHEJIANG UNIV
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